US6187384B1 - Aqueous binder dispersion useful for producing hardly yellowing, highly glossy coatings - Google Patents
Aqueous binder dispersion useful for producing hardly yellowing, highly glossy coatings Download PDFInfo
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- US6187384B1 US6187384B1 US09/043,090 US4309098A US6187384B1 US 6187384 B1 US6187384 B1 US 6187384B1 US 4309098 A US4309098 A US 4309098A US 6187384 B1 US6187384 B1 US 6187384B1
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- alkyd resin
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- polyurethane
- aqueous dispersion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
Definitions
- the invention relates to aqueous binder dispersions for preparing high-gloss coatings which are low in yellowing, comprising polyurethane alkyd resin components with a specific content and a specific combination of polyunsaturated fatty acid substituents as polymer side chains, and to their use as coating compositions, especially for wood and plastic.
- Aqueous polyurethane dispersions have long been known as binders in the preparation of coatings on metallic, mineral, wood or plastic substrates.
- polyurethane resin dispersions having a segment structure of the polymer backbone which leads to a two-phase or more-than-two-phase character and, associated therewith, to excellent elastic properties of the resins have been described (cf. e.g.: Dr. H.-P. Klein and Dr. M. Schwab, Kunststoffharz-Nachzin 29, pages 38 to 42, 1993).
- long-chain polyether-, polyester- or polycarbonate-polyol units form the soft segments and urethane units, formed from diisocyanate, glycol and dihydroxycarboxylic acid, the hard segments.
- oxidatively drying polyurethane-alkyd resin hybrids which carry unsaturated fatty acids as substituents and which are employed, in particular, in the field of corrosion protection.
- DE-A 3901190 describes alkyd resins based on polyesterpolyols which are reacted with a 2,2-bis(hydroxymethyl)alkanecarboxylic acid and a diisocyanate component in a one-pot reaction so as to give a resin having a weight-average molecular weight Mw of from 10,000 to 70,000 daltons, an acid number of from 18 to 36 mg of KOH/g, which still contains free hydroxyl groups but no longer contains isocyanate groups, with from 45 to 100% of the carboxyl groups introduced into the resin being converted to carboxylate groups by addition of a base.
- DE-A 4326270 embraces two-component polyurethane coating compositions, especially for the preparation of multicoat finishes in the automotive sector, which comprise aqueous dispersions of water-soluble or water-dispersible binders having isocyanate-reactive groups, as well as polyisocyanates as crosslinking components.
- suitable binders are alkyd-free anionic polyesters, prepared from polyalcohols and polycarboxylic acids having hyroxyl numbers of between 10 and 200 mg of KOH/g, acid numbers of between 10 and 100 mg of KOH/g and number-average molecular weights Mn of between 1000 and 100,000 daltons.
- DE-A 4328092 describes emulsifier-free aqueous coating compositions which contain as binder a combination of (A) a mixture of one or more water-dilutable polyurethane resins and/or alkyd-urethane resins, which may contain unsaturated fatty acid residues as substituents, with one or more water-dilutable (meth)acrylate copolymers, polyurethane resins and/or polyester resins, and (B) one or more amino resins and one or more blocked polyisocyanates.
- the binders described have acid numbers of between 10 and 100 mg of KOH/g, hydroxyl numbers of between 10 and 150 mg of KOH/g and number-average molecular weights of between 2000 and 10,000 daltons.
- DE-A 4226243 describes water-dilutable coating compositions comprising (A) film-forming polymerpolyols in the form of aqueous dispersions of fatty acid-modified polyurethane resins and/or fatty acid-modified polyester resins (alkyd resins) with saturated and unsaturated fatty acid residues, and (B) polyisocyanates having more than one free isocyanate group, with or without the addition of one or more organic solvents and of the customary paint additives, such as pigments, fillers or rheological auxiliaries, as two-component coating compositions.
- paint binders based on alkyd resin with a specific combination of unsaturated fatty acids each containing at least two double bonds in the carbon chain, in the alkyd component of the paint binder, together with a reduced solvent content in the binder component, achieve these objects outstandingly.
- novel one-component coating materials comprise binders BM consisting essentially of a polyurethane alkyd resin component (A) composed of:
- the mixture (a) preferably consists of from 80 to 50 parts by weight of (a1) and, correspondingly, from 20 to 50 parts by weight of (a2), particularly preferably of from 80 to 60 parts by weight of (a1) and, correspondingly, from 20 to 40 parts by weight of (a2).
- linoleic acid is employed as component (a1) and C18 conjuene fatty acid as component (a2).
- polyesterpolyols (b1) which as alcohol units (b11) preferably contain aliphatic, cycloaliphatic and/or araliphatic alcohols having per molecule 1-6 hydroxyl groups attached to nonaromatic carbon atoms, and as acid units (b12) preferably contain aliphatic, cycloaliphatic saturated or unsaturated and/or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids or their anhydrides or esters.
- the polyesterpolyols preferably possess acid numbers of between 1 and 10 mg of KOH/g, particularly preferably between 2 and 5 mg of KOH/g, and preferably hydroxyl numbers of between 100 and 250 mg of KOH/g, particularly preferably between 140 and 160 mg of KOH/g.
- Preferred polyisocyanates (b2) for the introduction of the urethane groups into the polyester main chain have 4 to 25 carbon atoms and 2 to 4 isocyanate groups per molecule.
- the polyurethane alkyd resin components (A) preferably have acid numbers of between 15 and 40 mg of KOH/g, particularly preferably between 20 and 30 mg of KOH/g, and preferably hydroxyl numbers of between 90 and 150 mg of KOH/g, particularly preferably between 100 and 130 mg of KOH/g.
- the content of urethane groups in the polyurethane alkyd resin components (A) is preferably between 5 and 15% by weight based on (A), particularly preferably between 5 and 10% by weight.
- the aqueous binder dispersions BM preferably contain less than 2% by weight of solvents, particularly preferably less than 1% by weight based on the binder dispersion BM.
- the aqueous binder dispersions BM may contain between 0 and 20% by weight, preferably between 0 and 10% by weight, based on (A), of additional crosslinking components (B), which are preferably able to react at room temperature with the excess hydroxyl and/or carboxyl groups of the polyurethane alkyd resin component (A).
- the mixture (a) which makes up the polymer side chains, consisting of unsaturated fatty acids (a1) having at least two nonconjugated double bonds and unsaturated fatty acids (a2) having at least two conjugated double bonds, is present in proportions of from 5 to 50% by weight, based on the polyurethane alkyd resin component (A), calculated as triglyceride (oil length), preferably in proportions of from 10 to 45% by weight.
- Components (a1) and (a2) are generally termed drying fatty acids and preferably have between 6 and 30, particularly preferably between 8 and 24, carbon atoms per molecule.
- Examples which may be mentioned of the unsaturated fatty acids (a1) having at least two nonconjugated double bonds are: linolenic acid and, preferably, linoleic acid as C18 fatty acids.
- an example which may be mentioned of the unsaturated fatty acids (a2) having at least two conjugated double bonds, also called conjuene fatty acids, is preferably the conjugated linoleic acid having two double bonds, in conjugation, on the 9th and on the 11th carbon atom of the C17-alkyl chain of the C18 fatty acid.
- the fatty acids (a1) and (a2) are present, for example, in natural oils such as linseed oil, soya oil, safflower oil, cottonseed oil or castor oil, sunflower oil, groundnut oil, wood oil and ricinene oil.
- the fatty acids obtained therefrom are linseed oil fatty acid, safflower oil fatty acid, tallow oil fatty acid, cottonseed oil fatty acid, groundnut oil fatty acid, wood oil fatty acid, ricinenic fatty acid or, preferably, sunflower oil fatty acid.
- the polyurethane units (b) which make up the polymer main chain are composed of polyesterpolyols (b1) and polyisocyanates (b2) such that the content of urethane groups in the polyurethane alkyd resins is preferably between 5 and 15% by weight based on (A), particularly preferably between 5 and 10% by weight based on (A).
- the acid numbers of the polyesterpolyols (b1) are preferably between 1 and 10 mg of KOH/g, particularly preferably between 2 and 5 mg of KOH/g, while the hydroxyl number of the polyesterpolyols (b1) is preferably between 100 and 250 mg of KOH/g, particularly preferably between 140 and 160 mg of KOH/g.
- the number-average molecular weights Mn of the polyesterpolyols are between 800 and 2000 daltons, preferably between 1000 and 1500 daltons.
- the polyesterpolyols (b1) are composed of alcohol units (b11) and acid units (b12).
- Preferred alcohol units (b11) used are aliphatic, cycloaliphatic and/or araliphatic alcohols having 1 to 6, preferably 1 to 4, hydroxyl groups attached to nonaromatic carbon atoms. Examples which may be mentioned of (b12) are:
- ethylene glycol propane-1,2- and -1,3-diol, butane-1,2-, -1,3- and -1,4-diol, 2-ethylpropane-1,3-diol, 2-methylpropanediol, 2-butyl-2-ethylpropanediol, 2-ethylhexane-1,3-diol, 1,3-neopentylglycol, 2,2-dimethylpentane-1,3-diol, hexane-1,6-diol, cyclohexane-1,2- and -1,4-diol, 1,2- and 1,4-bis(hydroxymethyl)cyclohexane, bis(4-hydroxycyclohexyl)methane, adipic acid bis(ethylene glycol ester), ether alcohols, such as di- and triethylene glycol, dipropylene glycol, perhydrogenated bisphenols, butane-1,2,
- At least some of the monomer units (b11) employed are polyols containing anionic groups or groups which can be converted into anionic groups, such as, for example, carboxyl groups.
- polyols containing anionic groups or groups which can be converted into anionic groups such as, for example, carboxyl groups.
- alkanoic acids having one to two hydroxyl substituents.
- These polyols generally have 1 to 3, preferably one carboxyl group in the molecule, and preferably 3 to 15 carbon atoms per molecule. Examples of such compounds are: hydroxypivalic acid, dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid and/or dihydroxycyclohexanemonocarboxylic acid.
- monomer unit is given to the 2,2-dimetylolalkanoic acids having alkyl radicals of up to 20 carbon atoms, for example 2,2-dimethylolacetic acid, 2,2-dimethylolpentanoic acid or, with very particular preference, 2,2-dimethylolpropionic acid.
- the proportion of carboxyl-containing monomers in the entirety of the polyol units (b11) is chosen such that the acid number of the polyurethane alkyd resin component (A) is preferably between 15 and 40 mg of KOH/g, particularly preferably between 20 and 30 mg of KOH/g.
- acid units (b12) it is preferred to employ aliphatic, cycloaliphatic saturated or unsaturated and/or aromatic polybasic carboxylic acids, particularly preferably di-, tri- and tetracarboxylic acid, and their anhydrides and/or their esters.
- phthalic acid anhydride
- isophthalic acid terephthalic acid, tetrahydro- or hexahydrophthalic acid (anhydride)
- endomethylenetetrahydrophthalic acid succinic acid, glutaric acid, sebacic acid, azelaic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid (anhydride), fumaric and maleic acid.
- isophthalic acid and phthalic acid (anhydride) isophthalic acid and phthalic acid (anhydride).
- Preferred polyisocyanates (b2) are those having 4 to 25 carbon atoms and 2 to 4 isocyanate groups per molecule. Particular preference is given to aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanates, for example: 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 2,2- and 2,6-diisocyanato-1-methylcyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 2,5- and 3,5-bis(isocyanatomethyl)-8
- aliphatic or cycloaliphatic polyisocyanates such as, in particular, hexamethylene diisocyanate, 4,4′-di(isocyanatocyclohexyl)methane and isophorone diisocyanate, and the araliphatic tetramethylxylylene diisocyanate.
- the polyurethane alkyd resins (A) are preferably prepared in a two-stage or more-than-two-stage process comprising first of all the synthesis of the polyesterpolyol component (b1), containing the unsaturated fatty acids (a1) and (a2) as monomer units, after which (b1) is reacted in a further process step with the polyisocyanate (b2) to give the polyurethane alkyd resin component.
- component (b1) which can also be termed hydroxy-functional alkyd resin
- component (b1) is carried out in the presence of from 0.01 to 2.5% by weight, based on the alkyd resin component (b1), of catalysts such as, preferably, dialkyl- or dialkoxytin oxides with azeotropic removal of the water of reaction by distillation, such that the alkyd resin (b1) has an acid number of preferably less than 10 mg of KOH/g, particularly preferably of less than 5 mg of KOH/g.
- the component (b1) prepared in this way is reacted, in a further process step, with the polyisocyanate (b2) in proportions by weight such that the resulting polyurethane alkyd resin (A) has a content of urethane groups of preferably between 5 and 15% by weight based on (A), particularly preferably between 5 and 10% by weight.
- the reaction is preferably continued until free isocyanate can no longer be detected.
- the acid number of the polyurethane alkyd resin (A) is preferably between 15 and 40 mg of KOH/g, particularly preferably between 20 and 30 mg of KOH/g, while the hydroxyl group number is preferably between 90 and 150 mg of KOH/g, particularly preferably between 100 and 130 mg of KOH/g.
- the polyisocyanates (b2) are preferably reacted with hydroxycarboxylic acids as contained, for example, in the above list for the synthesis of the hydroxyfunctional alkyd resin (b1). This is used, preferably, to control the acid number in the polyurethane alkyd resin (A).
- the number-average molecular weights Mn (determined by gel permeation chromatography) of the polyurethane alkyd resins (A) are generally between 1000 and 100,000, preferably between 2000 and 50,000, particularly preferably between 2000 and 20,000, daltons.
- the solution of the polyurethane alkyd resin (A) is then neutralized, preferably with a preferably organic base, for example ammonia or organic amines, such as triethylamine, N-methylmorpholine or amino alcohols, such as dimethylisopropanolamine, 2-amino-2-methylpropan-1-ol or, preferably, dimethylethanolamine.
- a preferably organic base for example ammonia or organic amines, such as triethylamine, N-methylmorpholine or amino alcohols, such as dimethylisopropanolamine, 2-amino-2-methylpropan-1-ol or, preferably, dimethylethanolamine.
- a preferably organic base for example ammonia or organic amines, such as triethylamine, N-methylmorpholine or amino alcohols, such as dimethylisopropanolamine, 2-amino-2-methylpropan-1-ol or, preferably, dimethylethanolamine.
- the solvents used for the preparation of the polyurethane alkyd resin (A) are preferably inert toward isocyanate and are water-dilutable, such as, for example, ketones, esters or ethers, for example acetone, N-methylpyrrolidone, dipropylene glycol dimethyl ether, ethyl ethoxypropionate or, with particular preference, methyl ethyl ketone.
- water-dilutable solvents which are not inert toward isocyanate, such as, for example, monofunctional alcohols, for example butanol, n-propanol, isopropanol; ether alcohols, for example butoxyethanol, methoxypropanol, ethoxypropanol, butoxypropanol; dialcohols, for example ethylene glycol; trialcohols, for example glycerol.
- monofunctional alcohols for example butanol, n-propanol, isopropanol
- ether alcohols for example butoxyethanol, methoxypropanol, ethoxypropanol, butoxypropanol
- dialcohols for example ethylene glycol
- trialcohols for example glycerol.
- solvents which are dilutable in water only slightly, if at all, and are inert toward isocyanate, such as ethers, esters, etheresters or ketones.
- the binder BM may include, in addition to the polyurethane alkyd resin component (A), resins different from (A), such as, for example, (meth)acrylic copolymers, polyester resins and/or polyurethane resins other than (A).
- resins different from (A) such as, for example, (meth)acrylic copolymers, polyester resins and/or polyurethane resins other than (A).
- the binders BM are aqueous dispersions and contain less than 5% by weight, preferably less than 2% by weight and, with particular preference, less than 1% by weight of solvent.
- the proportion of component (A) in the binder BM is between 20 and 75% by weight, preferably between 25 and 65% by weight and, with particular preference, between 30 and 60% by weight.
- novel one-component coating material contains at least one inorganic and/or organic color pigment or special-effect pigment and, if desired, a filler as well.
- color-imparting pigments or fillers examples include: titanium dioxide, iron oxide pigments, carbon blacks, silica, aluminum silicate, anticorrosion pigments, such as lead compounds and chromate compounds, barium sulfate, mica, talc, kaolin, chalk, azo dye pigments, phthalocyanine dye pigments or ultramarine blue.
- special-effect pigments are: metal pigments, for example of aluminum, copper or other metals, interference pigments, for. example metal oxide-coated metallic pigments, coated micas, for example titanium oxide-coated mica, and graphite effect pigments.
- the pigments are generally employed in the form of a paste which is, for example, commercially customary or is formulated, preferably, by combining some of the binder resin, water, wetting agent and pigment, together if desired with a filler, and is ground in equipment familiar to the person skilled in the art, for example a bead mill, to a defined pigment particle size, preferably between 10 and 15 micrometers. In this context it must be ensured that, during the milling process, the stability of the aqueous dispersion is retained. If appropriate, further dispersion auxiliaries can be added for this purpose.
- the weight ratio of pigment to binder is in general between 0.01:1 and 4:1, preferably between 0.3:1 and 1:1.
- the coating material generally comprises rheology-controlling agents such as, for example, polymer microparticles, inorganic phyllosilicates, for example aluminum-magnesium phyllosilicates, sodium-magnesium phyllosilicates and sodium-magnesium-fluorolithium phyllosilicates of the montmorillonite type, and associated thickeners, based for example on polyurethane or cellulose, or polyvinyl alcohol, poly(meth)acrylamide or polymers containing ionic groups, for example poly(meth)acrylic acid.
- rheology-controlling agents such as, for example, polymer microparticles, inorganic phyllosilicates, for example aluminum-magnesium phyllosilicates, sodium-magnesium phyllosilicates and sodium-magnesium-fluorolithium phyllosilicates of the montmorillonite type, and associated thickeners, based for example on polyurethane or cellulose,
- the novel coating formulations may contain components (B) which at the application temperatures crosslink the binders chemically, in other words with the formation of covalent bonds.
- the components (B) preferably react with the free hydroxyl groups of the polyurethane alkyd resin (A) with formation of a three-dimensional network.
- crosslinking components (B) are: polyisocyanates, as listed as component (b2) of the polyurethane alkyd resin (A), or polyepoxides.
- novel coating formulations are applied to the substrates to be coated by means of the techniques which are customary per se, such as, for example, dipping, knife coating, rolling or spraying, in the course of which the film which forms becomes crosslinked.
- Crosslinking takes place at temperatures between 0 and 100 degrees C., preferably between 10 and 60 degrees C., particularly preferably between 15 and 40 degrees C. (room temperature conditions).
- the film thicknesses of the novel coating materials applied depend on the application and on the coating formulation.
- clearcoat finishes have film thicknesses of between 40 and 100 micrometers
- pigmented basecoats or topcoats have film thicknesses of between 50 and 120 micrometers
- filler coatings or coatings to protect against mechanical impact stress have film thicknesses of between 70 and 160 micrometers
- primers have film thicknesses of between 50 and 110 micrometers.
- Suitable substrates for the novel coating formulations are any desired substrates, for example metal substrates such as iron, steels, aluminum or zinc.
- Suitable nonmetallic substrates which may be mentioned are mineral substrates, for example concrete, plasters or glass, wood or plastics, for example polyolefins, polyurethanes, polystyrene, polycarbonate, poly(meth)acrylates or polyvinyl chloride. If desired, the substrates may possess existing coatings.
- the novel coating formulations can be applied, alone or together with other coating compositions, in one or more steps. In applying the coating material it can be applied to dried coated or to a wet coated substrate, it being possible in the case of the latter technique to interpose a short flash-off phase. In the case of the multistep coating technique the novel coating material can be applied on its own in two or more steps, it being possible for the coated substrate prepared in the preliminary step to be dry or wet.
- neopentylglycol 647 g of trimethylolpropane, 331 g of isophthalic acid, 308 g of hexahydrophthalic anhydride, 792 g of a mixture of commercially customary linoleic acid and C18 fatty acid with conjugated double bonds, the linoleic acid making up a proportion of 75% by weight and the C18 fatty acid with conjugated double bonds making up the proportion to supplement the mixture to 100% by weight, are heated in a reactor, in the presence of 0.48 g of dibutyltin oxide as catalyst and of 40 g of xylene as entraining agent, and with azeotropic removal of the reaction product water, until an acid number of 4 mg of KOH/g is reached. After cooling, the product is dissolved in 212 g of methyl ethyl ketone.
- the methyl ethyl ketone is then removed by azeotropic distillation to a residual content of 0.78% by weight, based on the end product, and the dispersion is adjusted with deionized water to a content of polyurethane alkyd resin (A) of 40% by weight.
- 18 g of the binder dispersion BM according to Example 2 are mixed, following the addition of 6 g of deionized water and 8.9 g of a commercially customary dispersant based on anionic and nonionic constituents (Disperse Ayd W22 R from Krahn Chemie GmbH), with 60 g of titanium dioxide pigment (rutile type R-HD2 R from Tioxide). This mixture is adjusted with deionized water to a solids content of 70% and dispersion is carried out to completion, in a bead mill, to a pigment particle diameter of from 10 to 15 micrometers.
- siccative mixture consisting of strontium octoate, cobalt octoate and calcium octoate (50% by weight solids content, Siccatol R 938 from AKZO), are dispersed in 64 g of the binder dispersion BM according to Example 2. Then 21 g of the white pigment paste according to Example 3, 4 g of butylglycol, 0.5 g of a commercially customary thickener (polyurethane-based, 25% by weight solids content, Rheolate R 278 from Kronos Titan GmbH) and 0.3 g of a commercially customary antifoam (polysiloxane-based, Byk R 024 from Byk Chemie) are added with stirring.
- a commercially customary thickener polyurethane-based, 25% by weight solids content, Rheolate R 278 from Kronos Titan GmbH
- a commercially customary antifoam polysiloxane-based, Byk R 024 from Byk Chemie
- a nonionic wax emulsion (Aquacer R 535 from Byk-Cera Chemie B.V.) and a digested mixture of 0.3 g of a Theological additive (Bentone R LT from Kronos Titan GmbH) and 3.3 g of deionized water are added with stirring. Subsequently, deionized water is used to establish an application viscosity of from 950 to 1050 mPas.
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- Polymers & Plastics (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19534361A DE19534361A1 (de) | 1995-09-15 | 1995-09-15 | Wäßrige Bindemitteldispersion zur Herstellung von vergilbungsarmen hochglänzenden Beschichtungen |
DE19534361 | 1995-09-15 | ||
PCT/EP1996/003626 WO1997010276A1 (de) | 1995-09-15 | 1996-08-17 | Wässrige bindemitteldispersion zur herstellung von vergilbungsarmen hochglänzenden beschichtungen |
Publications (1)
Publication Number | Publication Date |
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US6187384B1 true US6187384B1 (en) | 2001-02-13 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/043,090 Expired - Fee Related US6187384B1 (en) | 1995-09-15 | 1996-08-17 | Aqueous binder dispersion useful for producing hardly yellowing, highly glossy coatings |
Country Status (8)
Country | Link |
---|---|
US (1) | US6187384B1 (uk) |
EP (1) | EP0850257B1 (uk) |
JP (1) | JP2000500165A (uk) |
AT (1) | ATE197161T1 (uk) |
BR (1) | BR9610490A (uk) |
CA (1) | CA2232035A1 (uk) |
DE (2) | DE19534361A1 (uk) |
WO (1) | WO1997010276A1 (uk) |
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US6620893B1 (en) | 1999-04-16 | 2003-09-16 | Bayer Aktiengesellschaft | Method of producing oxidative drying urethane-modified polyester dispersions and their use |
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US20030195305A1 (en) * | 2002-04-12 | 2003-10-16 | Thauming Kuo | Waterborne acetoacetate-functionalized alkyd coating compositions |
US6645613B1 (en) * | 1999-04-13 | 2003-11-11 | Spraylat Corporation | Coating compositions for use on substrates |
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US20040030038A1 (en) * | 2000-11-09 | 2004-02-12 | Joachim Woltering | Structurally viscous powder clearcoat slurry free from organic solvents and external emulsifiers, method for producing the same the use thereof |
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JP2010180299A (ja) * | 2009-02-04 | 2010-08-19 | Dic Corp | 酸化重合硬化型塗料用ドライヤー、塗料、及びその塗膜 |
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- 1996-08-17 EP EP96929268A patent/EP0850257B1/de not_active Expired - Lifetime
- 1996-08-17 AT AT96929268T patent/ATE197161T1/de not_active IP Right Cessation
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US6624238B1 (en) | 1998-09-12 | 2003-09-23 | Basf Coatings Ag | Intrinsically viscous clear powder coating slurry which is free of organic solvents and external emulsifiers, method for producing said slurry and use of the same |
US7019052B1 (en) | 1998-10-31 | 2006-03-28 | Basf Coatings Ag | Liquid substance mixtures and (co)-polymers, method for their production and use thereof for producing complex reactive mixtures |
US6747091B1 (en) | 1999-02-25 | 2004-06-08 | Basf Coatings Ag | Powder-slurry that can be hardened by actinic radiation or optionally by thermal means, method for producing said slurry and use of the same |
US7122595B1 (en) | 1999-02-25 | 2006-10-17 | Basf Coatings Ag | Powder-slurry that can be hardened by actinic radiation or by thermal means, method for producing said slurry and use of the same |
WO2005046888A1 (en) * | 1999-04-13 | 2005-05-26 | Spraylat Corporation | Coating compositions for use on substrates |
US6645613B1 (en) * | 1999-04-13 | 2003-11-11 | Spraylat Corporation | Coating compositions for use on substrates |
US6620893B1 (en) | 1999-04-16 | 2003-09-16 | Bayer Aktiengesellschaft | Method of producing oxidative drying urethane-modified polyester dispersions and their use |
US20030022985A1 (en) * | 2000-01-15 | 2003-01-30 | Ulrike Rockrath | Pseudoplastic powdered lacquer slurry free of organic solvents method for production and the use thereof |
US20050004301A1 (en) * | 2000-01-15 | 2005-01-06 | Ulrike Rockrath | Pseudoplastic powder lacquer slurry free of organic solvents, method for production and the use thereof |
US6943210B2 (en) | 2000-01-15 | 2005-09-13 | Basf Coatings Ag | Pseudoplastic powdered lacquer slurry free of organic solvents method for production and the use thereof |
US20030144413A1 (en) * | 2000-08-17 | 2003-07-31 | Gunther Ott | Pseudoplastic powdered lacquer slurry free of organic solvent and external emulsifiers, method for production and use thereof |
US20040030038A1 (en) * | 2000-11-09 | 2004-02-12 | Joachim Woltering | Structurally viscous powder clearcoat slurry free from organic solvents and external emulsifiers, method for producing the same the use thereof |
US7041729B2 (en) | 2000-11-09 | 2006-05-09 | Basf Coatings Ag | Structurally viscous powder clearcoat slurry free from organic solvents and external emulsifiers, method for producing the same the use thereof |
US20040030176A1 (en) * | 2001-09-05 | 2004-02-12 | Ohrbom Walter H. | Gamma hydroxy carbamate compounds and method of making and using the same |
US6780523B2 (en) * | 2002-04-12 | 2004-08-24 | Eastman Chemical Company | Waterborne acetoacetate-functionalized alkyd coating compositions |
US20030195305A1 (en) * | 2002-04-12 | 2003-10-16 | Thauming Kuo | Waterborne acetoacetate-functionalized alkyd coating compositions |
US20050238898A1 (en) * | 2002-05-03 | 2005-10-27 | Valspar Sourcing, Inc | Compliant overprint varnishes |
US7423093B2 (en) * | 2002-07-31 | 2008-09-09 | Basf Coatings Ag | Base paints containing fatty acid-modified epoxy esters, methods for the production thereof and their use |
US20060086927A1 (en) * | 2004-10-26 | 2006-04-27 | Don Kim H | Conductive paint compositions and methods of forming conductive coatings on substrates |
US7828994B2 (en) | 2004-10-26 | 2010-11-09 | Ortec, Inc. | Conductive paint compositions for forming conductive coatings on substrates |
KR100901198B1 (ko) | 2007-06-19 | 2009-06-08 | 코오롱패션머티리얼 (주) | 페놀성 황변 방지 폴리우레탄 필름의 제조 방법 |
US9156940B2 (en) | 2007-08-27 | 2015-10-13 | Valspar Sourcing, Inc. | Oxygen scavenging composition |
EP2188349A4 (en) * | 2007-08-27 | 2016-03-09 | Valspar Sourcing Inc | DEOXYGENANT COMPOSITION |
EP3296353A1 (de) | 2016-09-19 | 2018-03-21 | Daw Se | Lösemittelhaltige beschichtungsmasse für lackbeschichtungen |
EP3296353B1 (de) * | 2016-09-19 | 2022-01-26 | Daw Se | Lösemittelhaltige beschichtungsmasse für lackbeschichtungen |
FR3117857A1 (fr) * | 2020-12-21 | 2022-06-24 | L'oreal | Polymères alkyde biosourcé – polyuréthane en cosmétique |
Also Published As
Publication number | Publication date |
---|---|
DE59606056D1 (de) | 2000-11-30 |
JP2000500165A (ja) | 2000-01-11 |
BR9610490A (pt) | 1999-03-23 |
CA2232035A1 (en) | 1997-03-20 |
ATE197161T1 (de) | 2000-11-15 |
WO1997010276A1 (de) | 1997-03-20 |
DE19534361A1 (de) | 1997-03-20 |
EP0850257A1 (de) | 1998-07-01 |
EP0850257B1 (de) | 2000-10-25 |
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